TY  - GEN
A1  - Wolff, Christian Michael
A1  - Canil, Laura
A1  - Rehermann, Carolin
A1  - Nguyen, Ngoc Linh
A1  - Zu, Fengshuo
A1  - Ralaiarisoa, Maryline
A1  - Caprioglio, Pietro
A1  - Fiedler, Lukas
A1  - Stolterfoht, Martin
A1  - Kogikoski, Junior, Sergio
A1  - Bald, Ilko
A1  - Koch, Norbert
A1  - Unger, Eva L.
A1  - Dittrich, Thomas
A1  - Abate, Antonio
A1  - Neher, Dieter
T1  - Correction to 'Perfluorinated self-assembled monolayers enhance the stability and efficiency of inverted perovskite solar cells' (2020, 14 (2), 1445−1456)
T2  - ACS nano
Y1  - 2020
U6  - https://doi.org/10.1021/acsnano.0c08081
SN  - 1936-0851
SN  - 1936-086X
VL  - 14
IS  - 11
SP  - 16156
EP  - 16156
PB  - American Chemical Society
CY  - Washington, DC
ER  - 
TY  - JOUR
A1  - Mansour, Ahmed E.
A1  - Lungwitz, Dominique
A1  - Schultz, Thorsten
A1  - Arvind, Malavika
A1  - Valencia, Ana M.
A1  - Cocchi, Caterina
A1  - Opitz, Andreas
A1  - Neher, Dieter
A1  - Koch, Norbert
T1  - The optical signatures of molecular-doping induced polarons in poly(3-hexylthiophene-2,5-diyl)
BT  - individual polymer chains versus aggregates
JF  - Journal of materials chemistry : C, Materials for optical and electronic devices
N2  - Optical absorption spectroscopy is a key method to investigate doped conjugated polymers and to characterize the doping-induced charge carriers, i.e., polarons. For prototypical poly(3-hexylthiophene-2,5-diyl) (P3HT), the absorption intensity of molecular dopant induced polarons is widely used to estimate the carrier density and the doping efficiency, i.e., the number of polarons formed per dopant molecule. However, the dependence of the polaron-related absorption features on the structure of doped P3HT, being either aggregates or separated individual chains, is not comprehensively understood in contrast to the optical absorption features of neutral P3HT. In this work, we unambiguously differentiate the optical signatures of polarons on individual P3HT chains and aggregates in solution, notably the latter exhibiting the same shape as aggregates in solid thin films. This is enabled by employing tris(pentafluorophenyl)borane (BCF) as dopant, as this dopant forms only ion pairs with P3HT and no charge transfer complexes, and BCF and its anion have no absorption in the spectral region of P3HT polarons. Polarons on individual chains exhibit absorption peaks at 1.5 eV and 0.6 eV, whereas in aggregates the high-energy peak is split into a doublet 1.3 eV and 1.65 eV, and the low-energy peak is shifted below 0.5 eV. The dependence of the fraction of solvated individual chains versus aggregates on absolute solution concentration, dopant concentration, and temperature is elucidated, and we find that aggregates predominate in solution under commonly used processing conditions. Aggregates in BCF-doped P3HT solution can be effectively removed upon simple filtering. From varying the filter pore size (down to 200 nm) and thin film morphology characterization with scanning force microscopy we reveal the aggregates' size dependence on solution absolute concentration and dopant concentration. Furthermore, X-ray photoelectron spectroscopy shows that the dopant loading in aggregates is higher than for individual P3HT chains. The results of this study help understanding the impact of solution pre-aggregation on thin film properties of molecularly doped P3HT, and highlight the importance of considering such aggregation for other doped conjugated polymers in general.
Y1  - 2020
U6  - https://doi.org/10.1039/c9tc06509a
SN  - 2050-7526
SN  - 2050-7534
VL  - 8
IS  - 8
SP  - 2870
EP  - 2879
PB  - Royal Society of Chemistry
CY  - Cambridge
ER  - 
TY  - JOUR
A1  - Zu, Fengshuo
A1  - Schultz, Thorsten
A1  - Wolff, Christian Michael
A1  - Shin, Dongguen
A1  - Frohloff, Lennart
A1  - Neher, Dieter
A1  - Amsalem, Patrick
A1  - Koch, Norbert
T1  - Position-locking of volatile reaction products by atmosphere and capping layers slows down photodecomposition of methylammonium lead triiodide perovskite
JF  - RSC Advances
N2  - The remarkable progress of metal halide perovskites in photovoltaics has led to the power conversion efficiency approaching 26%. However, practical applications of perovskite-based solar cells are challenged by the stability issues, of which the most critical one is photo-induced degradation. Bare CH3NH3PbI3 perovskite films are known to decompose rapidly, with methylammonium and iodine as volatile species and residual solid PbI2 and metallic Pb, under vacuum under white light illumination, on the timescale of minutes. We find, in agreement with previous work, that the degradation is non-uniform and proceeds predominantly from the surface, and that illumination under N-2 and ambient air (relative humidity 20%) does not induce substantial degradation even after several hours. Yet, in all cases the release of iodine from the perovskite surface is directly identified by X-ray photoelectron spectroscopy. This goes in hand with a loss of organic cations and the formation of metallic Pb. When CH3NH3PbI3 films are covered with a few nm thick organic capping layer, either charge selective or non-selective, the rapid photodecomposition process under ultrahigh vacuum is reduced by more than one order of magnitude, and becomes similar in timescale to that under N-2 or air. We conclude that the light-induced decomposition reaction of CH3NH3PbI3, leading to volatile methylammonium and iodine, is largely reversible as long as these products are restrained from leaving the surface. This is readily achieved by ambient atmospheric pressure, as well as a thin organic capping layer even under ultrahigh vacuum. In addition to explaining the impact of gas pressure on the stability of this perovskite, our results indicate that covalently "locking" the position of perovskite components at the surface or an interface should enhance the overall photostability.
Y1  - 2020
U6  - https://doi.org/10.1039/d0ra03572f
SN  - 2046-2069
VL  - 10
IS  - 30
SP  - 17534
EP  - 17542
PB  - Royal Society of Chemistry
CY  - Cambridge
ER  - 
TY  - JOUR
A1  - Zu, Fengshuo
A1  - Wolff, Christian Michael
A1  - Ralaiarisoa, Maryline
A1  - Amsalem, Patrick
A1  - Neher, Dieter
A1  - Koch, Norbert
T1  - Unraveling the Electronic Properties of Lead Halide Perovskites with Surface Photovoltage in Photoemission Studies
JF  - ACS applied materials & interfaces
N2  - The tremendous success of metal-halide perovskites, especially in the field of photovoltaics, has triggered a substantial number of studies in understanding their optoelectronic properties. However, consensus regarding the electronic properties of these perovskites is lacking due to a huge scatter in the reported key parameters, such as work function (Φ) and valence band maximum (VBM) values. Here, we demonstrate that the surface photovoltage (SPV) is a key phenomenon occurring at the perovskite surfaces that feature a non-negligible density of surface states, which is more the rule than an exception for most materials under study. With ultraviolet photoelectron spectroscopy (UPS) and Kelvin probe, we evidence that even minute UV photon fluxes (500 times lower than that used in typical UPS experiments) are sufficient to induce SPV and shift the perovskite Φ and VBM by several 100 meV compared to dark. By combining UV and visible light, we establish flat band conditions (i.e., compensate the surface-state-induced surface band bending) at the surface of four important perovskites, and find that all are p-type in the bulk, despite a pronounced n-type surface character in the dark. The present findings highlight that SPV effects must be considered in all surface studies to fully understand perovskites’ photophysical properties.
KW  - lead halide perovskite films
KW  - ultraviolet photoelectron spectroscopy
KW  - Kelvin probe
KW  - surface band bending
KW  - surface photovoltage
KW  - surface states
Y1  - 2019
U6  - https://doi.org/10.1021/acsami.9b05293
SN  - 1944-8244
SN  - 1944-8252
VL  - 11
IS  - 24
SP  - 21578
EP  - 21583
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Zu, Fengshuo
A1  - Amsalem, Patrick
A1  - Egger, David A.
A1  - Wang, Rongbin
A1  - Wolff, Christian Michael
A1  - Fang, Honghua
A1  - Loi, Maria Antonietta
A1  - Neher, Dieter
A1  - Kronik, Leeor
A1  - Duhm, Steffen
A1  - Koch, Norbert
T1  - Constructing the Electronic Structure of CH3NH3PbI3 and CH3NH3PbBr3 Perovskite Thin Films from Single-Crystal Band Structure Measurements
JF  - The journal of physical chemistry letters
N2  - Photovoltaic cells based on halide perovskites, possessing remarkably high power conversion efficiencies have been reported. To push the development of such devices further, a comprehensive and reliable understanding of their electronic properties is essential but presently not available. To provide a solid foundation for understanding the electronic properties of polycrystalline thin films, we employ single-crystal band structure data from angle-resolved photoemission measurements. For two prototypical perovskites (CH3NH3PbBr3 and CH3NH3PbI3), we reveal the band dispersion in two high-symmetry directions and identify the global valence band maxima. With these benchmark data, we construct "standard" photoemission spectra from polycrystalline thin film samples and resolve challenges discussed in the literature for determining the valence band onset with high reliability. Within the framework laid out here, the consistency of relating the energy level alignment in perovskite-based photovoltaic and optoelectronic devices with their functional parameters is substantially enhanced.
Y1  - 2019
U6  - https://doi.org/10.1021/acs.jpclett.8b03728
SN  - 1948-7185
VL  - 10
IS  - 3
SP  - 601
EP  - 609
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Caprioglio, Pietro
A1  - Zu, Fengshuo
A1  - Wolff, Christian Michael
A1  - Prieto, Jose A. Marquez
A1  - Stolterfoht, Martin
A1  - Becker, Pascal
A1  - Koch, Norbert
A1  - Unold, Thomas
A1  - Rech, Bernd
A1  - Albrecht, Steve
A1  - Neher, Dieter
T1  - High open circuit voltages in pin-type perovskite solar cells through strontium addition
JF  - Sustainable Energy & Fuels
N2  - The incorporation of even small amounts of strontium (Sr) into lead-base hybrid quadruple cation perovskite solar cells results in a systematic increase of the open circuit voltage (V-oc) in pin-type perovskite solar cells. We demonstrate via absolute and transient photoluminescence (PL) experiments how the incorporation of Sr significantly reduces the non-radiative recombination losses in the neat perovskite layer. We show that Sr segregates at the perovskite surface, where it induces important changes of morphology and energetics. Notably, the Sr-enriched surface exhibits a wider band gap and a more n-type character, accompanied with significantly stronger surface band bending. As a result, we observe a significant increase of the quasi-Fermi level splitting in the neat perovskite by reduced surface recombination and more importantly, a strong reduction of losses attributed to non-radiative recombination at the interface to the C-60 electron-transporting layer. The resulting solar cells exhibited a V-oc of 1.18 V, which could be further improved to nearly 1.23 V through addition of a thin polymer interlayer, reducing the non-radiative voltage loss to only 110 meV. Our work shows that simply adding a small amount of Sr to the precursor solutions induces a beneficial surface modification in the perovskite, without requiring any post treatment, resulting in high efficiency solar cells with power conversion efficiency (PCE) up to 20.3%. Our results demonstrate very high V-oc values and efficiencies in Sr-containing quadruple cation perovskite pin-type solar cells and highlight the imperative importance of addressing and minimizing the recombination losses at the interface between perovskite and charge transporting layer.
Y1  - 2019
U6  - https://doi.org/10.1039/c8se00509e
SN  - 2398-4902
VL  - 3
IS  - 2
SP  - 550
EP  - 563
PB  - Royal Society of Chemistry
CY  - Cambridge
ER  - 
TY  - JOUR
A1  - Stolterfoht, Martin
A1  - Caprioglio, Pietro
A1  - Wolff, Christian Michael
A1  - Marquez, Jose A.
A1  - Nordmann, Joleik
A1  - Zhang, Shanshan
A1  - Rothhardt, Daniel
A1  - Hörmann, Ulrich
A1  - Amir, Yohai
A1  - Redinger, Alex
A1  - Kegelmann, Lukas
A1  - Zu, Fengshuo
A1  - Albrecht, Steve
A1  - Koch, Norbert
A1  - Kirchartz, Thomas
A1  - Saliba, Michael
A1  - Unold, Thomas
A1  - Neher, Dieter
T1  - The impact of energy alignment and interfacial recombination on the internal and external open-circuit voltage of perovskite solar cells
JF  - Energy & environmental science
N2  - Charge transport layers (CTLs) are key components of diffusion controlled perovskite solar cells, however, they can induce additional non-radiative recombination pathways which limit the open circuit voltage (V-OC) of the cell. In order to realize the full thermodynamic potential of the perovskite absorber, both the electron and hole transport layer (ETL/HTL) need to be as selective as possible. By measuring the photoluminescence yield of perovskite/CTL heterojunctions, we quantify the non-radiative interfacial recombination currents in pin- and nip-type cells including high efficiency devices (21.4%). Our study comprises a wide range of commonly used CTLs, including various hole-transporting polymers, spiro-OMeTAD, metal oxides and fullerenes. We find that all studied CTLs limit the V-OC by inducing an additional non-radiative recombination current that is in most cases substantially larger than the loss in the neat perovskite and that the least-selective interface sets the upper limit for the V-OC of the device. Importantly, the V-OC equals the internal quasi-Fermi level splitting (QFLS) in the absorber layer only in high efficiency cells, while in poor performing devices, the V-OC is substantially lower than the QFLS. Using ultraviolet photoelectron spectroscopy and differential charging capacitance experiments we show that this is due to an energy level mis-alignment at the p-interface. The findings are corroborated by rigorous device simulations which outline important considerations to maximize the V-OC. This work highlights that the challenge to suppress non-radiative recombination losses in perovskite cells on their way to the radiative limit lies in proper energy level alignment and in suppression of defect recombination at the interfaces.
Y1  - 2019
U6  - https://doi.org/10.1039/c9ee02020a
SN  - 1754-5692
SN  - 1754-5706
VL  - 12
IS  - 9
SP  - 2778
EP  - 2788
PB  - Royal Society of Chemistry
CY  - Cambridge
ER  - 
TY  - JOUR
A1  - Hörmann, Ulrich
A1  - Zeiske, Stefan
A1  - Park, Soohyung
A1  - Schultz, Thorsten
A1  - Kickhoefel, Sebastian
A1  - Scherf, Ullrich
A1  - Blumstengel, Sylke
A1  - Koch, Norbert
A1  - Neher, Dieter
T1  - Direct observation of state-filling at hybrid tin oxide/organic interfaces
JF  - Applied physics letters
N2  - Electroluminescence (EL) spectra of hybrid charge transfer states at metal oxide/organic type-II heterojunctions exhibit bias-induced spectral shifts. The reasons for this phenomenon have been discussed controversially and arguments for either electric field-induced effects or the filling of trap states at the oxide surface have been put forward. Here, we combine the results of EL and photovoltaic measurements to eliminate the unavoidable effect of the series resistance of inorganic and organic components on the total voltage drop across the hybrid device. For SnOx combined with the conjugated polymer [ladder type poly-(para-phenylene)], we find a one-to-one correspondence between the blue-shift of the EL peak and the increase of the quasi-Fermi level splitting at the hybrid heterojunction, which we unambiguously assign to state filling. Our data are resembled best by a model considering the combination of an exponential density of states with a doped semiconductor. Published under license by AIP Publishing.
Y1  - 2019
U6  - https://doi.org/10.1063/1.5082704
SN  - 0003-6951
SN  - 1077-3118
VL  - 114
IS  - 18
PB  - American Institute of Physics
CY  - Melville
ER  - 
TY  - JOUR
A1  - Zhang, Shanshan
A1  - Stolterfoht, Martin
A1  - Armin, Ardalan
A1  - Lin, Qianqian
A1  - Zu, Fengshuo
A1  - Sobus, Jan
A1  - Jin, Hui
A1  - Koch, Norbert
A1  - Meredith, Paul
A1  - Burn, Paul L.
A1  - Neher, Dieter
T1  - Interface Engineering of Solution-Processed Hybrid Organohalide Perovskite Solar Cells
JF  - ACS applied materials & interfaces
N2  - Engineering the interface between the perovskite absorber and the charge-transporting layers has become an important method for improving the charge extraction and open-circuit voltage (V-OC) of hybrid perovskite solar cells. Conjugated polymers are particularly suited to form the hole-transporting layer, but their hydrophobicity renders it difficult to solution-process the perovskite absorber on top. Herein, oxygen plasma treatment is introduced as a simple means to change the surface energy and work function of hydrophobic polymer interlayers for use as p-contacts in perovskite solar cells. We find that upon oxygen plasma treatment, the hydrophobic surfaces of different prototypical p-type polymers became sufficiently hydrophilic to enable subsequent perovskite junction processing. In addition, the oxygen plasma treatment also increased the ionization potential of the polymer such that it became closer to the valance band energy of the perovskite. It was also found that the oxygen plasma treatment could increase the electrical conductivity of the p-type polymers, facilitating more efficient charge extraction. On the basis of this concept, inverted MAPbI(3) perovskite devices with different oxygen plasma-treated polymers such as P3HT, P3OT, polyTPD, or PTAA were fabricated with power conversion efficiencies of up to 19%.
KW  - organohalide lead perovskites
KW  - solar cells
KW  - surface wetting
KW  - work function
KW  - oxygen plasma
KW  - transport layer
Y1  - 2018
U6  - https://doi.org/10.1021/acsami.8b02503
SN  - 1944-8244
VL  - 10
IS  - 25
SP  - 21681
EP  - 21687
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Hörmann, Ulrich
A1  - Zeiske, Stefan
A1  - Piersimoni, Fortunato
A1  - Hoffmann, Lukas
A1  - Schlesinger, Raphael
A1  - Koch, Norbert
A1  - Riedl, Thomas
A1  - Andrienko, Denis
A1  - Neher, Dieter
T1  - Stark effect of hybrid charge transfer states at planar ZnO/organic interfaces
JF  - Physical review : B, Condensed matter and materials physics
N2  - We investigate the bias dependence of the hybrid charge transfer state emission at planar heterojunctions between the metal oxide acceptor ZnO and three donor molecules. The electroluminescence peak energy linearly increases with the applied bias, saturating at high fields. Variation of the organic layer thickness and deliberate change of the ZnO conductivity through controlled photodoping allow us to confirm that this bias-induced spectral shift relates to the internal electric field in the organic layer rather than the filling of states at the hybrid interface. We show that existing continuum models overestimate the hole delocalization and propose a simple electrostatic model in which the linear and quadratic Stark effects are explained by the electrostatic interaction of a strongly polarizable molecular cation with its mirror image.
Y1  - 2018
U6  - https://doi.org/10.1103/PhysRevB.98.155312
SN  - 2469-9950
SN  - 2469-9969
VL  - 98
IS  - 15
PB  - American Physical Society
CY  - College Park
ER  -